Reactivity of a mixed methyl–aminobenzyl guanidinate lutetium complex towards iPrN＝C＝NiPr, CS2 and Ph2PH.

A heteroleptic terminal alkyl lutetium complex stabilized by a bulky guanidinato ligand, LLu(CH2C6H4NMe2-o)(Me)(THF) (1) (L = (PhCH2)2NC(NC6H3iPr2-2,6)2) has been synthesized by the treatment of LLu(CH2C6H4NMe2-o)2 with AlMe3 (1 equiv.) via an alkyl-exchange reaction in toluene/THF (4 : 1) solution and fully characterized. The difference in the activities of aminobenzyl and methyl was also proven through their selective reactivity, including complex 1 with one equivalent of DIC, CS2 and HPPh2, to afford complexes LLu[(NiPr2)2CMe](CH2C6H4NMe2-o) (2), L2Lu2[μ-η1:η2-S2C＝CHC6H4NMe2-o][μ-η2:η2-S2C＝CHC6H4NMe2-o](THF) (4), and {LLu(Me)[μ-O(CH2)4 PPh2]}2 (5), respectively. The subsequent transformations have also been investigated, obtaining complexes LLu[(NiPr2)2CMe][(NiPr2)2C CH2C6H4NMe2-o] (3), {LLu[O(CH2)4PPh2][μ-O(CH2)4PPh2]}2 (6) and dimeric lutetium phosphide {LLu[μ-O(CH2)4PPh2]}2(Me)(PPh2) (7). In addition, the guanidinate bimetallic alkynyl-bridged lutetium complex [LLu(μ-C≡CPh)]2(μ-η2:η2-PhC4Ph) (8) bearing the μ2-butatrienediyl group was obtained from the reaction of 1 with PhC≡CH (2 equiv.). The guanidinate lutetium μ-imido complex [LLu(μ-NPh)(THF)]2 (10) was also obtained in good yield by the treatment of 1 with PhNH2. [ABSTRACT FROM AUTHOR]